Composition for dyeing keratinous fibers comprising at least one diamino-N,N-dihydropyrazolone derivative

ABSTRACT

Disclosed herein are a composition for dyeing keratinous fibers, for example, human keratinous fibers such as hair, comprising at least one oxidation base chosen from diamino-N,N-dihydropyrazolone derivative and a method using the composition. Further disclosed herein are amino-N,N-dihydropyrazolone derivatives and the addition salts thereof and diamino-N,N-dihydropyrazolone derivatives and the addition salts thereof, as well as the methods for preparing these compounds.

This application claims benefit of U.S. Provisional Application No.60/527,778, filed Dec. 9, 2003, and U.S. Provisional Application No.60/549,535, filed Mar. 4, 2004.

Disclosed herein are a composition for dyeing keratinous fibers, forexample, human keratinous fibers such as hair, comprising at least oneoxidation base chosen from diamino-N,N-dihydropyrazolone derivatives andthe addition salts thereof and a method using the composition. Alsodisclosed herein are amino-N,N-dihydropyrazolone derivatives anddiamino-N,N-dihydropyrazolone derivatives and the addition saltsthereof, as well as methods of preparing these compounds.

It is known to dye keratinous fibers, for example, human keratinousfibers such as hair, with dyeing compositions containing oxidation dyeprecursors, such as ortho- and para-phenylenediamines, ortho- andpara-aminophenols, and heterocyclic compounds such as diaminopyrazolederivatives, pyrazolo[1,5-a]pyrimidine derivatives, pyrimidinederivatives, pyridine derivatives, 5,6-dihydroxyindole derivatives, and5,6-dihydroxyindoline derivatives, all of which are generally calledoxidation bases. Oxidation dye precursors or oxidation bases arecolorless or weakly colored compounds which, when combined withoxidizing products, can give rise, through a process of oxidativecondensation, to colored or coloring compounds.

It is also known that it is possible to vary the shades obtained withthese oxidation bases by combining them with couplers or colormodifiers, wherein the couplers or color modifiers are chosen, forexample, from meta-phenylenediamines, meta-aminophenols,meta-hydroxyphenols and certain heterocyclic compounds such aspyrazolo[1,5-b]-1,2,4-triazole derivatives,pyrazolo[3,2-c]-1,2,4-triazole derivatives, pyrazolo[1,5-a]pyrimidinederivatives, pyridine derivatives, pyrazol-5-one derivatives, indolinederivatives and indole derivatives.

The variety of molecules used in oxidation bases and couplers allows arich pallet of colors to be obtained.

The so-called “permanent” color obtained using these oxidation dyesshould satisfy a number of requirements. Thus, it should be withoutdrawbacks from the toxicological point of view, it should make itpossible to obtain shades in the desired intensity and exhibit goodresistance towards external agents such as light, adverse weatherconditions, washing, permanent waving, perspiration, and rubbing.

The dyes should also make it possible to cover grey hair, and should beas unselective as possible, i.e., making it possible to obtain thesmallest possible differences in color right along the same keratinousfiber, which may indeed be differently sensitized (i.e., damaged)between its tip and its root. The dyes should also have good chemicalstability in their formulations and have a good toxicological profile.

The use of an oxidation base such as para-phenylenediamine orpara-aminophenol derivatives makes it possible to obtain a fairly broadrange of colors having a basic pH, but without, however, achievingshades of good chromaticity while at the same time conferring on hairexcellent properties chosen from color intensity, shade variety, coloruniformity and resistance to external agents.

The use of these oxidation bases having a neutral pH may furthermore beineffective for obtaining a range of varied shades, such as forobtaining warm shades.

It has already been proposed in patent DE 3843892 to use certaindiaminopyrazole derivatives, in particular for red to coppery redshades. However, this proposal does not make it possible to obtain goodproperties of chromaticity and of resistance to external agents such aswashing and light. Furthermore, the breadth of the range of shades islimited.

Now, the present inventors have discovered, completely by surprise, thatnovel diamino-N,N-dihydropyrazolone compounds of formula (I) aresuitable for use as oxidation dye precursors and make it possible toobtain a color with varied shades, which can be at least one of intense,chromatic, aesthetic, not very selective and can be quite resistant tothe various attacks to which the hair may be subjected, such asshampoos, light, sweat and permanent waving.

The present inventors have also discovered, surprisingly, that thecolors obtained at neutral pH using such compounds can be intense.

Therefore, disclosed herein is a composition for dyeing keratinousfibers comprising, in an appropriate dyeing medium, at least oneoxidation base chosen from diamino-N,N-dihydropyrazolone derivatives offormula (I) and the addition salts and solvates thereof:

wherein:

R₁, R₂, R₃ and R₄, which are identical or different, are each chosenfrom:

linear and branched C₁-C₆ alkyl radicals optionally substituted with atleast one radical chosen from a radical OR₅, a radical NR₆R₇, a carboxylradical, a sulphonic radical, a carboxamido radical CONR₆R₇, asulphonamido radical SO₂NR₆R₇, heteroaryl radicals, and aryl radicalsoptionally substituted with at least one radical chosen from(C₁-C₄)alkyl, hydroxyl, C₁-C₂ alkoxy, amino, and (di)alkyl(C₁-C₂)aminoradicals;

aryl radicals optionally substituted with at least one radical chosenfrom (C₁-C₄)alkyl, hydroxyl, C₁-C₂ alkoxy, amino, and(di)alkyl(C₁-C₂)amino radicals; and

5- and, 6-membered heteroaryl radicals optionally substituted with atleast one radical chosen from (C₁-C₄)alkyl and (C₁-C₂)alkoxy radicals;

R₃ and R₄ may also be a hydrogen atom;

R₅, R₆ and R₇, which are identical or different, are each chosen from ahydrogen atom; linear and branched C₁-C₄ alkyl radicals optionallysubstituted with at least one radical chosen from a hydroxyl radical,C₁-C₂ alkoxy radicals, carboxamido radicals CONR₈R₉, sulphonyl radicalsSO₂R₈, and aryl radicals optionally substituted with at least oneradicals chosen from (C₁-C₄)alkyl, hydroxyl, C₁-C₂ alkoxy, amino, and(di)alkyl(C₁-C₂)amino radicals; and aryl radicals optionally substitutedwith at least one radical chosen from (C₁-C₄)alkyl, hydroxyl, C₁-C₂alkoxy, amino, and (di)alkyl(C₁-C₂)amino radicals;

R₆ and R₇, which are identical or different, may also be chosen fromcarboxamido radicals CONR₈R₉ and sulphonyl radicals SO₂R₈;

R₈ and R₉, which are identical or different, are each chosen from ahydrogen atom; linear and branched C₁-C₄ alkyl radicals optionallysubstituted with at least one radical chosen from hydroxyl and C₁-C₂alkoxy radicals;

R₁ and R₂, as well as R₃ and R₄, on the other hand, may, respectively,form, with the nitrogen atoms to which they are attached, a heterocyclechosen from saturated and unsaturated 5- to 7-membered heterocyclesoptionally substituted with at least one entity chosen from halogenatoms, and amino, (di)alkyl(C₁-C₄)amino, hydroxyl, carboxyl, carboxamidoand (C₁-C₂)alkoxy radicals, and C₁-C₄ alkyl radicals optionallysubstituted with at least one radical chosen from hydroxyl, amino,(di)alkylamino, alkoxy, carboxyl and sulphonyl radicals;

R₃ and R₄ may also form, together with the nitrogen atom to which theyare attached, a heterocycle chosen from 5- and 7-membered heterocycleswhose carbon atoms may be replaced with at least one optionallysubstituted atom chosen from optionally substituted oxygen and nitrogenatoms.

The present disclosure makes it possible, for example, to obtain a coloron keratinous fibers which is fast and resistant to light and towashing.

Further disclosed herein is a method for dyeing keratinous fibers usingthe inventive composition, and the use of this composition for dyeingkeratinous fibers.

Even further disclosed herein are novel amino-N,N-dihydropyrazolonederivatives of formula (I′) and diamino-N,N-dihydropyrazolonederivatives of formula (I″), and the addition salts thereof, as well asnovel methods of preparing these compounds.

As indicated above, the composition as disclosed herein comprises atleast one oxidation base chosen from diamino-N,N-dihydropyrazolonederivatives of formula (I) and the addition salts and solvates thereof.

In one embodiment, in formula (I), the radicals R₁ and R₂, which areidentical or different, are chosen from

-   -   C₁-C₄ alkyl radicals optionally substituted with at least one        radical chosen from hydroxyl, (C₁-C₂)alkoxy, amino, and        (di)alkyl(C₁-C₂)amino radicals; and    -   a phenyl radical.

In another embodiment, the radicals R₁ and R₂, which are identical ordifferent, are chosen from methyl, ethyl, 2-hydroxyethyl,3-hydroxypropyl, 2-hydroxypropyl and phenyl radicals.

According to another embodiment, the radicals R₁ and R₂ form, togetherwith the nitrogen atoms to which they are attached, a saturated orunsaturated, optionally substituted, 5- or 6-membered ring.

For example, the radicals R₁ and R₂ form, together with the nitrogenatoms to which they are attached, a pyrazolidine or pyridazolidine ringoptionally substituted with at least one radical chosen from C₁-C₄alkyl, hydroxyl, (C₁-C₂)alkoxy, carboxyl, carboxamido, amino, and(di)alkyl(C₁-C₂)amino radicals.

In another embodiment, the radicals R₁ and R₂ form, together with thenitrogen atoms to which they are attached, a pyrazolidine orpyridazolidine ring.

The radicals R₃ and R₄, which are identical or different, are, forexample, chosen from a hydrogen atom; linear and branched C₁-C₄ alkylradicals optionally substituted with at least one radical chosen fromhydroxyl, (C₁-C₂)alkoxy, amino, and (di)alkyl(C₁-C₂)amino radicals; aphenyl radical optionally substituted with at least one radical chosenfrom hydroxyl, amino and (C₁-C₂)alkoxy radicals.

In one embodiment, the radicals R₃ and R₄, which are identical ordifferent, are chosen from a hydrogen atom, and methyl, ethyl,isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl and2-carboxyethyl radicals. According to one embodiment, the radicals R₃and R₄ are each a hydrogen atom.

According to another embodiment, the radicals R₃ and R₄ form, togetherwith the nitrogen atom to which they are attached, a 5- or 7-memberedring chosen from pyrrolidine, piperidine, homopiperidine, piperazine andhomopiperazine heterocycles; wherein it is possible for the rings to besubstituted with at least one radical chosen from hydroxyl, amino,(di)alkyl(C₁-C₂)amino, carboxyl and carboxamido radicals, and C₁-C₄alkyl radicals optionally substituted with at least one radical chosenfrom hydroxyl, amino, and C₁-C₂ (di)alkylamino radicals.

In another embodiment, the radicals R₃ and R₄ form, together with thenitrogen atom to which they are attached, a 5- or 7-membered ring chosenfrom pyrrolidine, 2,5-dimethylpyrrolidine, pyrrolidine-2-carboxylicacid, 3-hydroxypyrrolidine-2-carboxylic acid,4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine,3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine,3-hydroxy-2-carboxamidopyrrolidine, 2-(diethylcarboxamido)pyrrolidine,2-hydroxymethylpyrrolidine, 3,4-dihydroxy-2-hydroxymethylpyrrolidine,3-hydroxypyrrolidine, 3,4-dihydroxypyrrolidine, 3-aminopyrrolidine,3-methylaminopyrrolidine, 3-dimethylaminopyrrolidine,4-amino-3-hydroxypyrrolidine,3-hydroxy-4-(2-hydroxyethyl)aminopyrrolidine, piperidine,2,6-dimethyl-piperidine, 2-carboxypiperidine, 2-carboxamidopiperidine,2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine,3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine,homopiperidine, 2-carboxyhomopiperidine, 2-carboxamido-homopiperidine,homopiperazine, N-methylhomopiperazine, andN-(2-hydroxyethyl)homopiperazine.

In one embodiment, the radicals R₃ and R₄ form, together with thenitrogen atom to which they are attached, a 5- or 7-membered ring chosenfrom pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine,3-dimethylaminopyrrolidine, pyrrolidine-2-carboxylic acid,3-hydroxypyrrolidine-2-carboxylic acid, piperidine, hydroxypiperidine,homopiperidine, diazepane, N-methylhomopiperazine, andN-β-hydroxyethylhomopiperazine.

In accordance with one embodiment, the radicals R₃ and R₄ form, togetherwith the nitrogen atom to which they are attached, a 5-membered ringchosen, for example, from pyrrolidine, 3-hydroxypyrrolidine,3-aminopyrrolidine, and 3-dimethylaminopyrrolidine.

The compounds of formula (I) may be optionally salified with at leastone acid chosen from strong inorganic acids such as HCl, HBr, HI, H₂SO₄,H₃PO₄, and organic acids such as acetic, lactic, tartaric, citric andsuccinic, benzenesulphonic, para-toluenesulphonic, formic andmethanesulphonic acids.

The compounds of formula (I) may also be in the form of solvates, forexample, a hydrate or a solvate of a linear or branched alcohol such asethanol and isopropanol.

Examples of the compounds of formula (I) and the addition salts thereofinclude:

-   4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,-   4-amino-5-methylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,-   4-amino-5-dimethylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,-   4-amino-5-(2-hydroxyethyl)amino-1,2-dimethyl-1,2-dihydropyrazol-3-one,-   4-amino-5-(pyrrolidin-1-yl)-1,2-dimethyl-1,2-dihydropyrazol-3-one,-   4-amino-5-(piperidin-1-yl)-1,2-dimethyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,-   4-amino-5-methylamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,-   4-amino-5-dimethylamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,-   4-amino-5-(2-hydroxyethyl)amino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,-   4-amino-5-(pyrrolidin-1-yl)-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,-   4-amino-5-(piperidin-1-yl)-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,-   4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-1,2-phenyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-1-ethyl-2-methyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-2-ethyl-1-methyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-1-phenyl-2-methyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-1-(2-hydroxyethyl)-2-methyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-2-(2-hydroxyethyl)-1-methyl-1,2-dihydropyrazol-3-one,-   2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-methylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-(2-hydroxypropyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-bis(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-(3-hydroxypyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-(piperidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2,3-diamino-6-methyl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2,3-diamino-6-dimethyl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one,-   2,3-diamino-5,8-dihydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one,-   4-amino-5-dimethylamino-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-ethylamino-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-isopropylamino-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-(2-hydroxyethylamino)-1,2-dihydropyrazol-3-one,-   4-amino-5-(2-dimethylaminoethylamino)-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4-amino-5-[bis(2-hydroxyethyl)amino]-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-(3-imidazol-1-ylpropylamino)-1,2-dihydropyrazol-3-one,-   4-amino-5-dimethylamino-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-ethylamino-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-isopropylamino-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-(2-hydroxyethylamino)-1,2-dihydropyrazol-3-one,-   4-amino-5-(2-dimethylaminoethylamino)-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4-amino-5-[bis(2-hydroxyethyl)amino]-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-(3-imidazol-1-ylpropylamino)-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-(3-hydroxypyrrolidin-1-yl)-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-pyrrolidin-1-yl-1,2-dihydropyrazol-3-one,-   4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4-amino-1,2-diethyl-5-(4-methylpiperazin-1-yl)pyrazolidin-3-one, and-   2,3-diamino-6-hydroxy-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one,    some of which are presented below to illustrate their names by    chemical structures:

Among these compounds, examples of the diamino-N,N-dihydropyrazolonederivatives of formula (I) and their addition salts include:

-   2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,-   4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,-   2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,-   2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,    and-   2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one.

The at least one oxidation base as disclosed herein is generally presentin an amount ranging from 0.001 to 10%, such as from 0.005 to 6%, byweight relative to the total weight of the dyeing composition.

The dyeing composition as disclosed herein may comprise at least onecoupler chosen from the couplers conventionally used for dyeingkeratinous fibers. Among these couplers, mention may be made, forexample, of meta-phenylenediamines, meta-aminophenols, meta-diphenols,naphthalene couplers, heterocyclic couplers and their addition salts.

By way of example, the at least one coupler may be chosen from2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol,6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxybenzene,1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline,3-ureido-1-dimethylaminobenzene, sesamol,1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol,2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine,6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine,1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene,2,6-bis(β-hydroxyethylamino)toluene and the acid addition salts thereof.

In the composition as disclosed herein, the at least one coupler isgenerally present in an amount ranging from 0.001 to 10%, such as from0.005 to 6%, by weight relative to the total weight of the dyeingcomposition.

The composition as disclosed herein may further comprise at least oneadditional oxidation base chosen from oxidation bases conventionallyused in oxidation dyeing other than those described above. By way ofexample, the at least one additional oxidation base is chosen frompara-phenylenediamines, bisphenylalkylenediamines, para-aminophenols,bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines, andheterocyclic bases different from the compounds of formula (I) asdefined above and their addition salts.

Among the para-phenylenediamines, there may be mentioned, by way ofexample, para-phenylenediamine, para-tolylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine,N-(D-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine,2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene,3-hydroxy-1-(4′-aminophenyl)pyrrolidine and the acid addition saltsthereof.

Among the para-phenylenediamines mentioned above, examples includepara-phenylenediamine, para-tolylenediamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine,2-O-acetylaminoethyloxy-para-phenylenediamine, and the acid additionsalts thereof.

Among the bisphenylalkylenediamines, there may be mentioned, by way ofexample,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)-tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylene-diamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the acid addition saltsthereof.

Among the para-aminophenols, there may be mentioned, by way of example,para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol, andthe acid addition salts thereof.

Among the ortho-aminophenols, there may be mentioned, by way of example,2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol,5-acetamido-2-aminophenol, and the acid addition salts thereof.

Among the heterocyclic bases, there may be mentioned, by way of example,pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, there may be mentioned the compoundsdescribed, for example, in patents GB 1,026,978 and GB 1,153,196, aswell as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine,2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine,and the acid addition salts thereof.

Other pyridine oxidation bases useful in the present disclosure include,for example, the oxidation bases 3-aminopyrazolo[1,5-a]pyridines andtheir addition salts which are described, for example, in patentapplication FR 2801308. By way of example, there may be mentionedpyrazolo[1,5-a]pyridin-3-ylamine;2-acetylaminopyrazolo[1,5-a]pyridin-3-ylamine;2-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine;3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid;2-methoxypyrazolo[1,5-a]pyridin-3-ylamino;(3-aminopyrazolo[1,5-a]pyridin-7-yl)methanol;2-(3-aminopyrazolo[1,5-a]pyridin-5-yl)methanol;2-(3-aminopyrazolo[1,5-a]pyridin-7-yl)ethanol;(3-aminopyrazolo[1,5-a]pyridin-2-yl)methanol;3,6-diaminopyrazolo[1,5-a]pyridine; 3,4-diaminopyrazolo[1,5-a]pyridine;pyrazolo[1,5-a]pyridine-3,7-diamine;7-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine;pyrazolo[1,5-a]pyridine-3,5-diamine;5-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine;2-[(3-aminopyrazol[1,5-a]pyridin-5-yl)(2-hydroxyethyl)amino]ethanol;2-[(3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxyethyl)amino]ethanol,3-aminopyrazolo[1,5-a]pyridin-5-ol; 3-aminopyrazolo[1,5-a]pyridin-5-ol,3-aminopyrazolo[1,5-a]pyridin-6-ol; 3-aminopyrazolo[1,5-a]pyridin-7-ol;and the acid and base addition salts thereof.

Among the pyrimidine derivatives, there may be mentioned the compoundsdescribed, for example, in patents DE 2,359,399; JP 88-169,571; JP05-63124; and EP 0770375 and patent application WO 96/15765, such as2,4,5,6-tetraminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,2,5,6-triaminopyrimidine, and the pyrazolopyrimidine derivatives such asthose mentioned in patent application FR-A-2,750,048 and among whichthere may be mentioned, for example,pyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;pyrazolo[1,5-a]pyrimidine-3,5-diamine;2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;3-aminopyrazolo[1,5-a]pyrimidin-7-ol;3-aminopyrazolo[1,5-a]pyrimidin-5-ol;2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol,2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol,2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol,2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol,5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine andtheir acid addition salts and their tautomeric forms, when a tautomericequilibrium exists.

Among the pyrazole derivatives, there may be mentioned the compoundsdescribed in, for example, patents DE 3,843,892, DE 4,133,957 and patentapplications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988such as 4,5-diamino-1-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole,4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the acidaddition salts thereof.

The at least one additional oxidation base in the composition asdisclosed herein is generally present in an amount ranging from 0.001 to10%, such as from 0.005 to 6%, by weight relative to the total weight ofthe dyeing composition.

In general, the addition salts of the oxidation bases and couplers whichcan be used in the context of the present disclosure are, for example,chosen from the addition salts with an acid such as hydrochlorides,hydrobromides, sulphates, citrates, succinates, tartrates, lactates,tosylates, benzenesulphonates, phosphates and acetates and the additionsalts with a base such as sodium hydroxide, potassium hydroxide,ammonium hydroxide, amines and alkanolamines.

The dyeing composition as disclosed herein may, in addition, comprise atleast one direct dye chosen, for example, from nitro dyes of the benzeneseries, azo direct dyes and methine direct dyes. These direct dyes maybe of a nonionic, anionic or cationic nature.

The medium appropriate for dyeing, also called the dye carrier, is acosmetic medium generally comprising water or a mixture of water and atleast one organic solvent for solubilizing the compounds which might notbe sufficiently soluble in water. The at least one organic solvent maybe chosen, for example, from lower C₁-C₄ alkanols, such as ethanol andisopropanol; polyols and polyol ethers such as 2-butoxyethanol,propylene glycol, propylene glycol monomethyl ether, diethylene glycolmonoethyl ether and monomethyl ether, and aromatic alcohols such asbenzyl alcohol and phenoxyethanol, and mixtures thereof.

The at least one organic solvent is, for example, present in an amountranging from 1 to 40%, such as from 5 to 30%, by weight relative to thetotal weight of the dyeing composition.

The dyeing composition as disclosed herein may also comprise at leastone adjuvant chosen from various adjuvants conventionally used in hairdyeing compositions, such as anionic, cationic, nonionic, amphoteric andzwitterionic surfactants and mixtures thereof, anionic, cationic,nonionic, amphoteric and zwitterionic polymers and mixtures thereof,inorganic and organic thickeners, such as the associative thickeners,anionic, cationic, nonionic and amphoteric polymers, antioxidants,penetrating agents, sequestrants, perfumes, buffers, dispersing agents,conditioning agents such as modified and unmodified, volatile andnonvolatile silicones, film-forming agents, ceramides, preservatives,and opacifying agents.

The at least one adjuvant is generally present in an amount ranging from0.01 to 20% by weight relative to the total weight of the dyeingcomposition.

Of course, persons skilled in the art will be careful to choose this orthese optional additional compounds such that the advantageousproperties intrinsically attached to the oxidation dyeing composition asdisclosed herein are not, or not substantially, impaired by theaddition(s) envisaged.

The pH of the dyeing composition as disclosed herein generally rangesfrom 3 to 12, such as from 5 to 11. It may be adjusted to the desiredvalue by at least one agent chosen from acidifying and alkalinizingagents customarily used in dyeing keratinous fibers or with the aid ofconventional buffering systems.

Among the acidifying agents, there may be mentioned, by way of example,inorganic or organic acids such as hydrochloric acid, orthophosphoricacid, sulphuric acid, carboxylic acids such as acetic acid, tartaricacid, citric acid, lactic acid, and sulphonic acids.

Among the alkalinizing agents, there may be mentioned, by way ofexample, ammonium hydroxide, alkali metal carbonates, alkanolamines suchas mono-, di- and triethanolamines and the derivatives thereof, sodiumand potassium hydroxides and the compounds of the following formula(II):

wherein W is a propylene residue optionally substituted with at leastone radical chosen from hydroxyl and C₁-C₄ alkyl radicals; R_(a), R_(b),R_(c) and R_(d), which may be identical or different, are each chosenfrom a hydrogen atom, C₁-C₄ alkyl radicals and C₁-C₄ hydroxyalkylradicals.

The dyeing composition as disclosed herein may be provided in variousforms, such as in the form of liquids, creams and gels, or in any otherappropriate form for dyeing keratinous fibers, such as human hair.

The method disclosed herein comprises applying the composition accordingto the present disclosure, as defined above, to the keratinous fibers,in which the color is developed using at least one oxidizing agent. Thecolor may be developed at acidic, neutral or alkaline pH and theoxidizing agent may be added to the composition as disclosed herein justat the time of use or it can be used from an oxidizing compositioncontaining it, applied simultaneously or sequentially with thecomposition as disclosed herein.

In one embodiment, the composition as disclosed herein is mixed, such asat the time of use, with a composition comprising, in a mediumappropriate for dyeing, at least one oxidizing agent, wherein the atleast one oxidizing agent is present in a sufficient quantity to developa color. The mixture obtained is then applied to the keratinous fibers.After an exposure time ranging from 3 to 50 minutes, such as from 5 to30 minutes, the keratinous fibers are rinsed, washed with shampoo,rinsed again and then dried.

The at least one oxidizing agent is chosen from those conventionallyused for the oxidation dyeing of keratinous fibers, for example,hydrogen peroxide, urea peroxide, alkali metal bromates, persalts suchas perborates and persulphates, peracids and the oxidase enzymes, amongwhich there may be mentioned peroxidases, oxidoreductases with 2electrons such as uricases and oxygenases with 4 electrons such aslaccases. In one embodiment, hydrogen peroxide is used.

The oxidizing composition may also comprise at least one adjuvant chosenfrom various adjuvants conventionally used in hair dyeing compositionsand as defined above.

The pH of the oxidizing composition containing the oxidizing agent issuch that, after mixing with the dyeing composition, the pH of theresulting composition applied to keratinous fibers ranges, for example,from 3 to 12, such as from 5 to 11. It may be adjusted to the desiredvalue by at least one agent chosen from acidifying and alkalinizingagents customarily used for dyeing keratinous fibers and as definedabove.

The ready-to-use composition which is finally applied to the keratinousfibers may be provided in various forms, such as in the form of liquids,creams and gels, or in any other form appropriate for dyeing keratinousfibers, such as human hair.

Further disclosed herein is a multicompartment device or dyeing “kit” inwhich a first compartment comprises the dyeing composition as definedabove and a second compartment comprises an oxidizing composition. Thisdevice may be equipped with tools which make it possible to deliver thedesired mixture to the hair, such as the devices described in patentFR-2 586 913.

Using this device, it is possible to dye keratinous fibers using amethod, which comprises mixing the dyeing composition comprising atleast one oxidation base of formula (I) with at least one oxidizingagent, and applying the mixture obtained to the keratinous fibers for atime sufficient to develop the desired color.

Further disclosed herein is the use, for the oxidation dyeing ofkeratinous fibers, for example, human keratinous fibers such as hair, ofthe diamino-N,N-dihydropyrazolone derivative of formula (I) or of one ofits addition salts as defined above.

Even further disclosed herein are amino-N,N-dihydropyrazolonederivatives of the following formula (I′), and their addition salts:

wherein:R′₁, R′₂, R′₃ and R′₄ respectively have the same meanings as R₁, R₂, R₃and R₄, and R′₁₃ is chosen from nitro, nitroso and arylazo Ar—N═N—groups wherein the aryl radical Ar is optionally substituted with atleast one entity chosen from C₁-C₄ alkyl, amino, (di)alkyl(C₁-C₄)amino,C₁-C₂ alkoxy, sulphonic, and carboxyl radicals and halogen atoms,provided that

-   -   R′₁ and R′₂ are not simultaneously a methyl radical when R′₃ and        R′₄ are each a hydrogen atom and    -   R′₁₃ is not a group Ar—N═N— when R′₃ and R′₄ simultaneously are        each a hydrogen atom.

All that has been stated above regarding the definitions of the radicalsR₁, R₂, R₃ and R₄ applies to R′₁, R′₂, R′₃ and R′₄ and will not berepeated in this part of the text.

Further disclosed herein are diamino-N,N-dihydropyrazolone derivativesof the following formula (I″), and their addition salts:

wherein R″₁, R″₂, R″₃ and R″₄ have the same meanings as those statedabove for R′₁, R′₂, R′₃ and R′₄.

Here again, all that has been stated above regarding the definitions ofthe radicals R′₁, R′₂, R′₃ and R′₄ applies to R″₁, R″₂, R″₃ and R″₄ andwill not be repeated in this part of the text.

The amino-N,N-dihydropyrazolone derivatives anddiamino-N,N-dihydropyrazolone derivatives as disclosed herein, whereinthe radicals R′₃ and R′₄, as well as R″₃ and R″₄, respectively, are ahydrogen atom, may be obtained from intermediates and routes ofsynthesis described in the literature such as: J. Het. Chem., 2001,38(3), 613-616, Helvetica Chimica Acta, 1950, 33, 1183-1194, J. Org.Chem., 23, 2029 (1958), J. Am. Chem. Soc., 73, 3240 (1951), J. Am. Chem.Soc., 84, 590 (1962), Justus Liebig Ann. Chem., 686, 134 (1965),Tetrahedron Lett., 31, 2859-2862 (1973), and U.S. Pat. Nos. 4,128,425and 2,841,584 and the references cited therein.

According to these references, the compounds of formula (I) having R₃and R₄ equal to hydrogen atoms may be obtained from the route ofsynthesis represented in scheme A below:

The compounds as disclosed herein wherein R₁ and R₂ simultaneously areeach a methyl group and R₃ and R₄ simultaneously are each a hydrogenatom may be obtained based on the method described in Justus Lieb. Ann.Chem., 686, 134 (1965) (scheme B):

The compounds as disclosed herein wherein R₁ is a methyl group, R₂ is aphenyl radical, and R₃ and R₄ simultaneously are each a hydrogen atommay be obtained based on the method described in J. Org. Chem., 23, 2029(1958) and J. Am. Chem. Soc., 73, 3240 (1951) (scheme C):

The compounds as disclosed herein wherein R₁ and R₂ form together withthe nitrogen atoms to which they are attached a 5-membered ring and R₃and R₄ simultaneously are each a hydrogen atom may be obtained based onthe method described in J. Het. Chem., 2001, 38(3), 613-616 (scheme D):

According to a novel method disclosed herein, the compounds of formula(I) may be obtained according to the synthesis illustrated in scheme E:

This novel method comprises the following reactions:

-   -   a) reaction 1: a compound a        R₁HN—NHR₂  a    -   is reacted with a compound b:    -   to give a compound 5-amino-1,2-dihydropyrazol-3-one c:    -   b) reaction 2: the derivative c thus obtained is reacted with an        aryldiazonium salt (Ar—NH₂, NaNO₂, H^(⊕)) to give an azo        compound f:    -   c) reaction 3: functionalizing the primary amine group of the        resulting azo compound f is optionally carried out in order to        give the following compound    -   d) reaction 4: a reaction of reduction of the azo compound f or        g is carried out in order to obtain an amine-containing compound        e or h respectively:

The optional reaction of functionalizing the primary amine group at the5-position to a secondary and tertiary amine NR₃R₄ in order to give thecompounds g, is carried out according to conventional methods of organicsynthesis (alkyl halide, alkyl O-sulphonate, alkyl trialkylammonium,reductive amination, and the like, see for example Advanced OrganicChemistry, 3rd edition, 1985, J. March, Wiley Interscience).

The reduction of the azo group leads to compounds e and h in accordancewith the present disclosure.

The reduction is carried out in a conventional manner, for example, bycarrying out a hydrogenation reaction by heterogeneous catalysis in thepresence of Pd/C, Pd(II)/C, Ni/Ra, and the like or alternatively bycarrying out a reduction reaction with a metal, for example with zinc,iron, tin and the like (see Advanced Organic Chemistry, 3rd edition, J.March, 1985, Wiley Interscience and Reduction in Organic Chemistry, M.Hudlicky, 1983, Ellis Horwood Series Chemical Science).

According to a novel method disclosed herein, the2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-onederivatives in accordance with formula (I) are obtained according to thesynthesis illustrated by scheme F:

This novel method comprises the following reactions:

-   -   a) reaction 1: the following compound a1:    -   is reacted with a compound a2:    -   to give a compound a3:

wherein:

R₁₀ is chosen from a hydrogen atom, a carboxyl radical; a carboxamidoradical; C₁-C₄ alkyl radicals optionally substituted with at least oneradical chosen from hydroxyl, amino, (di)alkylamino, alkoxy, carboxyland sulphonyl radicals;

R₁₁ and R₁₂, which may be identical or different, are each chosen fromhydrogen and halogen atoms; an amino radical; (di)alkyl(C₁-C₄)aminoradicals; a hydroxyl radical; a carboxyl radical; a carboxamido radical;(C₁-C₂)alkoxy radicals; C₁-C₄ alkyl radicals optionally substituted withat least one radical chosen from hydroxyl, amino, (di)alkylamino,alkoxy, carboxyl and sulphonyl radicals;

X is chosen from halogen atoms and alkyl sulphonates;

r is an integer ranging from 1 to 3;

-   -   b) reaction 2: the compound a3 is reacted with an amine of        formula NHR₃R₄ to give a compound a4:    -   c) reaction 3: the compound a4 is reacted with at least one        compound chosen from alkylsulphonyl, arylsulphonyl and        perfluoroalkylsulphonyl halides R—O₂S—X, (wherein R is chosen        from alkyl, aryl and perfluoroalkyl radicals, and X₁ is chosen        from halogen atoms), in a solvent having a boiling point ranging        from 60° C. to 190° C. in order to give a compound a5:    -   d) reaction 4: the resulting compound a5 is then heated in a        solvent having a boiling point ranging from 60° C. to 190° C. to        give a compound a6:    -   e) reaction 5: the compound a6 obtained is reduced to give the        compound a7 of formula below (III):

For example, according to this method, 3,5-dibromo-4-nitropyrazole a1,obtained according to the method described, for example, in document DE4234885, reacts with the reagent a2, such as in a solvent having aboiling point ranging from 60° C. to 190° C. By way of example, theremay be mentioned pentanol, dimethylformamide, and N-methylpyrrolidine.In one embodiment, the reduction is carried out in the presence of atleast one base chosen from organic and inorganic bases, such as sodiumcarbonate, sodium hydroxide, sodium acetate and triethylamine. Thetemperature of the reaction medium is, for example, maintained at arange of from 60° C. to 160° C., such as from 80° C. to 120° C.

1-Hydroxyalkyl-3,5-dibromo-4-nitropyrazole a3 is, for example, isolatedby precipitation or crystallization after adding ice to the reactionmedium.

In reaction 2, the derivative a3 is reacted with an amine NHR₃R₄, forexample, in a solvent having a boiling point ranging from 60° C. to 190°C. such as butanol, pentanol, and dimethylformamide. The temperature mayrange, for example, from 60° C. to 160° C., such as from 80° C. to 120°C. After consuming the reagents, the compound5-amino-4-nitro-3-bromo-1-hydroxyalkylpyrazole a4 is isolated byprecipitation or crystallization using water.

In accordance with reaction 3, the derivative a5 is obtained by reactionof the alcohol a4 and of a compound chosen from alkylsulphonyl,arylsulphonyl and perfluoroalkylsulphonyl halides. The reaction takesplace, for example, in an aprotic solvent such as tetrahydrofuran anddioxane. In one embodiment, the reaction takes place at a temperatureranging from −20° C. to 60° C., such as from 0° C. to 25° C.Furthermore, this reaction takes place in the presence of at least onebase chosen from organic and inorganic bases such as potassiumcarbonate, triethylamine, and N-methylmorpholine. After thedisappearance of the reagents, compound a5 is isolated by precipitationor crystallization from water.

In reaction 4, the sulphonate a5 obtained at the end of reaction 3 isdissolved, or dispersed in a solvent having a boiling point ranging from60° C. to 190° C., such as from 90° C. to 140° C. The temperature of thereaction medium is then brought to a temperature ranging from 90° C. to140° C., such as from 105° C. to 125° C. until there is totalconsumption of the sulphonate a5. After returning to room temperature,the perhydropyrazolo[1,2-a]pyrazol-1-one (r=1),perhydropyridazino[1,2-a]pyrazol-1-one (r=2) orperhydrodiazepino[1,2-a]pyrazolone (r=3) compound a6 crystallizes and isisolated by conventional methods of organic synthesis.

The final compound a7 in accordance with the present disclosure isobtained during reaction 5 by reducing the nitro derivative a6, whereinthe methods of reduction used include, for example, hydrogenation byheterogeneous catalysis in the presence of Pd/C, Pd(II)/C, Ni/Ra, andthe like or alternatively such as a reduction reaction with a metal, forexample, zinc, iron, tin and the like (see Advanced Organic Chemistry,3rd edition, J. March, 1985, Wiley Interscience and Reduction in OrganicChemistry, M. Hudlicky, 1983, Ellis Horwood Series Chemical Science).

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thisspecification and attached claims are approximations that may varydepending upon the desired properties sought to be obtained by thepresent disclosure. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should be construed in light of thenumber of significant digits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

The following non-limiting examples serve to illustrate the invention.

EXAMPLES Example 1 Synthesis of2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 5

Reaction 1: Synthesis of3-(3,5-dibromo-4-nitro-1H-pyrazol-1-yl)propan-1-ol 1

In a 500 ml three-necked flask, 0.369 mol of sodium acetate wasintroduced into a solution of 0.184 mol of dibromonitropyrazole in 250ml of N-methylpyrrolidone and the reaction medium was heated to 80° C.

At this temperature, 0.369 mol of 3-bromopropanol was added dropwise.This temperature was maintained for 5 hours.

After cooling to room temperature, the medium was poured over ice, withstirring.

3-(3,5-Dibromo-4-nitro-1H-pyrazol-1-yl)propan-1-ol 1 precipitated. Itwas drained, dried and obtained with a yield of 75%.

The mass of the expected compound C₆H₇Br₂N₃O₃ was detected by massspectrometry.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

Reaction 2: Synthesis of3-[5-(benzylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propan-1-ol 2

0.135 mol of 3-(3,5-dibromo-4-nitro-1H-pyrazol-1-yl)propan-1-ol 1 wasdispersed in a 500 ml three-necked flask containing 150 ml of ethanol,the medium was heated to 60° C. and then 0.825 mol of benzylamine wasadded over 30 minutes.

After 6 hours at 60° C., the reaction medium was cooled to roomtemperature.

3-[5-(Benzylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propan-1-ol 2 wasprecipitated by pouring the reaction medium over 1 liter of ice, withstirring. After draining and drying under vacuum in the presence ofP₂O₅, the compound 2 was isolated with a yield of 90%.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

Elemental analysis: Theoretical: C43.96 H4.26 N15.77 O13.51 Br22.50Measured: C44.09 H4.22 N15.44 O14.37 Br21.50

Reaction 3: Synthesis of3-[5-(benzylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 3

0.126 mol of3-[5-(benzylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propan-1-ol 2 and15.82 ml of triethylamine were introduced, with stirring, into a 500 mlthree-necked flask containing 200 ml of THF. The mixture obtained wasthen cooled to 5° C. and 0.126 mol of mesyl chloride were poured in over45 minutes.

The reaction medium was maintained at this temperature for 2 hours, andthen 3-[5-(benzylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 3 was precipitated by pouring the reaction medium over800 ml of ice.

After filtration, the solid was thoroughly washed with water and withdiisopropyl ether. Drying was carried out under vacuum in the presenceof P₂O₅. The yield of this reaction was 94%.

The mass of the expected compound C₁₄H₁₇BrN₄O₅S was detected by massspectrometry.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

Elemental analysis: Theory: C38.81 H3.96 N12.93 O18.46 S7.40 Br18.44Measured: C39.03 H3.91 N12.83 O18.52 S7.29 Br18.26

Reaction 4: Synthesis of3-(benzylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 4

0.1 mol of 3-[5-(benzylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 3 was dispersed, with stirring, in a 500 mlthree-necked flask containing 300 ml of pentanol and the reaction mediumwas heated at 130° C. for 2 hours.

After cooling to room temperature, the solid formed was drained onsintered glass, washed with diisopropyl ether and dried under vacuum inthe presence of P₂O₅.3-(Benzylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 4was obtained with a yield of 86%.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₆H₁₁N₄O was detected by massspectrometry.

Elemental analysis: Theory: C56.72 H5.49 N20.36 O17.44 Measured: C56.68H5.13 N20.38 O17.69

Reaction 5: Synthesis of2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 5

20 g of3-(benzylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 4and 4 g of 5% palladium on carbon were introduced into a 1 literautoclave containing 800 ml of ethanol. The reduction was then carriedout at a hydrogen pressure of 8 bar and at a temperature ranging from50° C. to 100° C. (stirring with a speed ranging from 1000 to 2500 rpm).

After 4 hours of reaction, there was no further consumption of hydrogenand the medium was cooled to 20° C.

The catalyst was removed under nitrogen by filtration, and thenhydrochloric ethanol was added to the filtrate. The crystallized productwas drained, washed with diisopropyl ether and then dried under vacuumin the presence of P₂O₅.2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 5 was obtained with a yield of 89%.

The mass of the expected compound was detected by mass spectrometry.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

Elemental analysis: Theoretical: C31.73 H5.33 N24.67 O7.07 Cl31.22Measured: C31.45 H5.20 N24.62 O7.24 Cl30.86

Example 2 Synthesis of2-amino-3-(ethylamino)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 9

Reaction 2: Synthesis of3-[3-bromo-5-(ethylamino)-4-nitro-1H-pyrazol-1-yl]propan-1-ol 6

15 mmol of 3-(3,5-dibromo-4-nitro-1H-pyrazol-1-yl)propan-1-ol in 30 mlof ethanol were introduced into a three-necked flask, with stirring. Thehomogeneous medium was heated to 75° C. and then 93 mmol of ethylaminewere poured in dropwise and the stirring was maintained for four hours.

After cooling to room temperature, the medium was poured over ice and3-[3-bromo-5-(ethylamino)-4-nitro-1H-pyrazol-1-yl]propan-1-ol 6precipitated.

The yellow solid was drained, and then thoroughly washed with water andwith diisopropyl ether. Drying was carried out under vacuum in thepresence of P₂O₅. The mass recovered is 3.6 g.

The NMR analyses (¹H400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₈H₁₃BrN₄O₃ was detected by massspectrometry.

Reaction 3: Synthesis of3-[5-(ethylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 7

11.2 mmol of3-[3-bromo-5-(ethylamino)-4-nitro-1H-pyrazol-1-yl]propan-1-ol 6 and 1.6ml of triethylamine were introduced, with stirring, into a 100 mlthree-necked flask containing 30 ml of THF. The orange-coloredhomogeneous mixture obtained was cooled to 0° C. and 1.44 ml of mesylchloride were poured in over 20 minutes.

The reaction medium was maintained at this temperature for 2 hours andthen 3-[5-(ethylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 7 was precipitated by pouring the reaction medium over500 ml of ice.

The yellow solid was drained, and then thoroughly washed with water andwith diisopropyl ether; drying was carried out under vacuum in thepresence of P₂O₅. The mass recovered is 3.1 g.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₉H₁₅BrN₄O₅S was detected by massspectrometry.

Reaction 4: Synthesis of3-(ethylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 8

8 mmol of 3-[5-(ethylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 7 were dispersed, with stirring, in a 50 mlthree-necked flask containing 20 ml of pentanol, and the reaction mediumwas heated at 130° C. for 2 hours.

After cooling to room temperature, the solid formed was drained, andthen washed with diisopropyl ether.

After drying under vacuum in the presence of P₂O₅, 1.46 g of3-(ethylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 8was obtained.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound was detected by mass spectrometry.

Reaction 5: Synthesis of2-amino-3-(ethylamino)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 9

1.45 g of3-(ethylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 8and 300 mg of 5% palladium on carbon were introduced into a 300 mlautoclave containing 200 ml of ethanol. The reduction was carried out ata hydrogen pressure of 8 bar at a temperature of 60° C. (stirring at1700 rpm).

After 2 hours of reaction, there was no further consumption of hydrogenand the medium was cooled to 20° C.

The catalyst was removed by filtration under nitrogen and the filtratewas diluted with 100 ml of hydrochloric isopropyl ether.

The pale yellow solution was evaporated to dryness and then the solidwas taken up in an ethanol/isopropyl ether mixture.2-Amino-3-(ethylamino)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 9 precipitated; it was drained and after drying undervacuum in the presence of P₂O₅, 1.18 g of2-amino-3-(ethylamino)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 9 were recovered.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₈H₁₄N₄O was detected by massspectrometry.

Example 32-amino-3-(isopropylamino)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 13

Reaction 2:3-[3-bromo-5-(isopropylamino)-4-nitro-1H-pyrazol-1-yl]propan-1-ol 10

15 mmol of 3-(3,5-dibromo-4-nitro-1H-pyrazol-1-yl)propan-1-ol in 30 mlof ethanol were introduced into a three-necked flask, with stirring. Thehomogeneous medium was heated to 75° C., and then 93 mmol ofisopropylamine were poured in dropwise while maintaining the stirringfor four hours.

After cooling to room temperature, the medium was poured over ice, andthen neutralized with hydrochloric acid.3-[3-Bromo-5-(isopropylamino)-4-nitro-1H-pyrazol-1-yl]propan-1-ol 10 wasextracted with dichloromethane.

After drying the organic phase over sodium sulphate and removing thesolvent by evaporation under vacuum, 4.37 g of3-[3-bromo-5-(isopropylamino)-4-nitro-1H-pyrazol-1-yl]propan-1-ol 10were obtained.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₉H₁₅BrN₄O₃ was detected by massspectrometry.

Reaction 3: Synthesis of3-[5-(isopropylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 11

13.7 mmol of3-[3-bromo-5-(isopropylamino)-4-nitro-1H-pyrazol-1-yl]propan-1-ol 10 and1.94 ml of triethylamine were introduced, with stirring, into a 50 mlthree-necked flask containing 20 ml of THF. The orange-coloredhomogeneous mixture thus obtained was cooled to 0° C. and 1.76 ml ofmesyl chloride were poured in over 20 minutes.

The reaction medium was maintained at this temperature for 2 hours andthen 3-[5-(ethylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 11 was precipitated by pouring the reaction mediumover 500 ml of ice.

The yellow solid was drained and then thoroughly washed with water andpetroleum ether, drying was carried out under vacuum in the presence ofP₂O₅. The mass recovered is 4.2 g.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound was detected by mass spectrometry.

Reaction 4: Synthesis of3-(isopropylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one12

10 mmol of 3-[5-(isopropylamino)-3-bromo-4-nitro-1H-pyrazol-1-yl]propylmethanesulphonate 11 in 20 ml of pentanol were dispersed, with stirring,in a 50 ml three-necked flask and the medium was heated at 130° C. for 2hours.

After cooling to room temperature, the solid obtained was drained onsintered glass, and washed with diisopropyl ether.

After drying under vacuum in the presence of P₂O₅, 1.71 g of3-(isopropylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one12 were obtained.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₉H₁₄N₄O₃ was detected by massspectrometry.

Reaction 5: Synthesis of2-amino-3-(isopropylamino)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 13

1.70 g of3-(isopropylamino)-2-nitro-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one12 and 300 mg of 5% palladium on carbon were introduced into a 300 mlautoclave containing 200 ml of ethanol. The reduction was carried out ata temperature of 60° C. and at a hydrogen pressure of 6 bar (stirring at2000 rpm).

After 2 hours of reaction, there was no further consumption of hydrogenand the medium was cooled to 20° C.

The catalyst was removed by filtration under nitrogen after cooling toroom temperature and hydrochloric isopropyl ether was added.

The pale yellow solution was evaporated to dryness and then the solidwas taken up in 50 ml of diisopropyl ether saturated with hydrochloricacid, the precipitate was recovered by draining. After drying undervacuum in the presence of P₂O₅, 1.5 g of2-amino-3-(isopropylamino)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 13 were isolated.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₉H₁₆N₄O was detected by massspectrometry.

Example 42-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 17

Reaction 2:3-(3-bromo-4-nitro-5-(pyrrolidin-1-yl)-1H-pyrazol-1-yl)propan-1-ol 14

15 mmol of 3-(3,5-dibromo-4-nitro-1H-pyrazol-1-yl)propan-1-ol in 20 mlof isopropanol were introduced into a three-necked flask, with stirring.The homogeneous medium was heated to 75° C. and then 90 mmol ofpyrrolidine were poured in dropwise and the stirring was maintained for2 hours.

After cooling to room temperature, the medium was poured over ice andneutralized with hydrochloric acid.3-(3-Bromo-4-nitro-5-(pyrrolidin-1-yl)-1H-pyrazol-1-yl)propan-1-ol 14was extracted with dichloromethane.

After drying of the organic phase over sodium sulphate and distillationof the solvent by evaporation under vacuum, 4.8 g of3-(3-bromo-4-nitro-5-(pyrrolidin-1-yl)-1H-pyrazol-1-yl)propan-1-ol 14were obtained.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₁₀H₁₇BrN₄O was detected by massspectrometry.

Reaction 3: Synthesis of3-(3-bromo-4-nitro-5-(pyrrolidin-1-yl)-1H-pyrazol-1-yl)propylmethanesulphonate 15

30 mmol of3-(3-bromo-4-nitro-5-(pyrrolidin-1-yl)-1H-pyrazol-1-yl)propan-1-ol 14and 4.25 ml of triethylamine were introduced, with stirring, into a 100ml three-necked flask containing 50 ml of THF. The orange-coloredhomogeneous mixture obtained was cooled to 0° C. and 2.32 ml of mesylchloride were poured in over 20 minutes.

The reaction medium was maintained at this temperature for 2 hours andthen 3-(3-bromo-4-nitro-5-(pyrrolidin-1-yl)-1H-pyrazol-1-yl)propylmethanesulphonate 15 was precipitated by pouring the reaction mediumover ice.

The solid was drained and then dried under vacuum in the presence ofP₂O₅. The mass recovered is 9.3 g.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₁₁H₁₉BrN₄O₃S was detected by massspectrometry.

Reaction 4: Synthesis of2-nitro-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one16

22.5 mmol of3-(3-bromo-4-nitro-5-(pyrrolidin-1-yl)-1H-pyrazol-1-yl)propylmethanesulphonate 15 in 100 ml of pentanol were introduced, withstirring, into a 250 ml three-necked flask. The medium thus obtained washeated at 130° C. for 2 hours.

After cooling to room temperature,2-nitro-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one16 was extracted with dichloromethane.

After drying of the organic phase over sodium sulphate and distillationof the solvent under vacuum, 1.2 g of2-nitro-3-pyrrolidin-1-yl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one16 were obtained.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₁₀H₁₄N₄O₃ was detected by massspectrometry.

Reaction 5: Synthesis of2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 17

1.1 g of2-nitro-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one16 and 300 mg of 5% palladium on carbon were introduced into a 300 mlautoclave containing 200 ml of ethanol. The reduction was carried outwith stirring at 2000 rpm, at a temperature of 60° C. and at a hydrogenpressure of 6 bar.

After 2 hours of reaction, there was no further consumption of hydrogenand the medium was cooled to 20° C.

The catalyst was removed by filtration under nitrogen after cooling toroom temperature and hydrochloric isopropyl ether was added.

The pale yellow solution was evaporated to dryness and then the solidwas taken up in 50 ml of diisopropyl ether saturated with hydrochloricacid, the precipitate was recovered by draining. After drying undervacuum in the presence of P₂O₅, 1.5 g of2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedihydrochloride 17 were obtained.

The NMR analyses (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) are inconformity with the expected structure.

The mass of the expected compound C₁₀H₁₆N₄O was detected by massspectrometry.

Example 5 Synthesis of2,3-diamino-6,7,-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedimethanesulphonate

Synthesis of3-amino-2-nitroso-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 2

In a 500 ml three-necked flask, 43 g (0.245 mol) of3-amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one hydrochloridewere dissolved at room temperature, with stirring, in a mixture of 180ml of water and 35 ml of 35% hydrochloric acid.

The medium was cooled to 0° C. and a solution of 17.3 g of sodiumnitrite (0.25 mol) in 20 ml of water was added dropwise over 30 minutes.The temperature of the reaction medium was maintained in a range from 0to +5° C. during the entire duration of the addition and for one hourafter the end of the addition.

The reaction medium was brought to pH 8 by addition of sodium hydroxide,with stirring, while maintaining the temperature in a range from 0 to 5°C.

3-Amino-2-nitroso-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 2precipitated in the form of a red-orange-colored solid which wasfiltered on No. 4 sintered glass, impasted in a minimum of 2-propanol,washed with diisopropyl ether and dried under vacuum in the presence ofphosphorus pentoxide. 35 g of an orange-red product were thus obtained(yield: 85%).

The NMR spectra (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) and mass spectraare in conformity with the expected structure 2.

Synthesis of 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedimethanesulphonate 3

33.6 g (0.2 mol) of3-amino-2-nitroso-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one 2, 500ml of ethanol and 6 g of 5% palladium on carbon containing 50% of waterwere introduced into a 1 liter autoclave.

The medium was purged 3 times with nitrogen and then 3 times withhydrogen and the temperature of the mixture was brought to 40° C.

The reduction was carried out over two hours at a pressure of 8 bar.This reduction was exothermic and the temperature reached 70° C. byitself.

The temperature was allowed to decrease to 50° C. and then the catalystwas filtered on a filter press under a nitrogen stream.

The filtrate was poured into a mixture of 50 ml of ethanol and 40 ml ofmethanesulphonic acid, while cooling to 0° C.2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedimethanesulphonate 3 crystallized in the form of a pale yellow solidwhich was drained on No. 4 sintered glass, washed with diisopropyl etherand then with petroleum ether, and finally dried under vacuum in thepresence of phosphorus pentoxide. 43 g of a pale yellow solid were thusobtained (yield: 65%).

The NMR spectra (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) and mass spectraare in conformity with the expected structure 3.

Elemental analysis: Theory: C27.74 H5.23 N16.17 O32.33 S18.51 Measured:C27.16 H5.22 N15.63 O32.81 S18.64

Example 6 Synthesis of2,3-diamino-5,6,7,8-tetrahydro-1H-pyrazolo[1,2-a]pyridazin-1-onehydrochloride

Synthesis of di-tert-butyl tetrahydropyridazine-1,2-dicarboxylate A

50 ml of toluene, 5 g (21.5 mmol) ofN,N′-di-tert-butoxycarbonylhydrazide, 680 mg of tetraethylammoniumbromide and 25 ml of 50% sodium hydroxide were introduced, withmechanical stirring, into a 250 ml three-necked flask equipped with acondenser, a thermometer and a dropping funnel.

The heterogeneous medium was heated to 100° C. and then1,4-dibromobutane was added dropwise over 15 minutes.

The reaction medium was heated at 100° C. for 3 days. After cooling, 100ml of ethyl acetate were added and the medium was transferred into aseparating funnel. The organic phase was washed with 4×70 ml of asaturated aqueous sodium carbonate solution, and then with 4×70 ml ofwater and finally with 4×70 ml of salt water. The organic phase wasdried over sodium sulphate and the solvent was evaporated under vacuum.A colorless oil was thus obtained which crystallized in the form of awhite solid.

A mass of 6.1 g is recovered (yield: 99%).

The NMR spectra (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) and mass spectraare in conformity with the expected structure A.

Synthesis of hexahydropyridazine dihydrochloride B

5.9 g of compound A in 50 ml of a 3/1 mixture of dioxane and 35%hydrochloric acid were introduced, with mechanical stirring, into a 100ml three-necked flask equipped with a condenser and a thermometer.

The colorless solution obtained was stirred at room temperature for 3hours and then the reaction medium was diluted with diisopropyl ether.The solvents were evaporated under vacuum. The pasty residue obtainedwas taken up in an ether/ethanol mixture. After filtration of the solidand drying under vacuum, 1.39 g of a white solid were obtained.

The NMR spectra (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) and mass spectraare in conformity with the expected structure B.

Synthesis of3-amino-5,6,7,8-tetrahydro-1H-pyrazolo[1,2-a]pyridazin-1-one C

7.5 ml of ethanol, 1.5 ml of triethylamine and 0.73 ml of3-amino-3-ethoxyacrylic acid were introduced, with mechanical stirring,into a 25 ml three-necked flask equipped with a condenser and athermometer. 500 mg of hexahydropyridazine dihydrochloride (compound B)were then added and the medium was stirred for 3 hours at roomtemperature.

The insoluble material was filtered and the solvent was distilled undervacuum. The solid was taken up in a minimum of water, filtered and driedunder vacuum. 0.9 g of a slightly yellow powder was obtained.

The NMR spectra (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) and mass spectraare in conformity with the expected structure C.

Synthesis of3-amino-2-nitroso-5,6,7,8-tetrahydro-1H-pyrazolo[1,2-a]pyridazin-1-one D

20 ml of hydrochloric acid at 35% and 1 g of3-amino-5,6,7,8-tetrahydro-1H-pyrazolo[1,2-a]pyridazin-1-one (compoundC) were introduced, with mechanical stirring, into a 50 ml three-neckedflask equipped with a condenser and a thermometer.

The medium was cooled to 0° C. and a solution of 675 mg of sodiumnitrite in 5 ml of water was poured in while maintaining thistemperature. The color of the reaction mixture changes from yellow toorange and a precipitate began to form.

Within 30 minutes, the reaction was complete and the orange solid wasfiltered on No. 4 sintered glass, washed with water and then dried undervacuum. The yield is 78.3%.

The NMR spectra (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) and mass spectraare in conformity with the expected structure D.

Synthesis of2,3-diamino-5,6,7,8-tetrahydro-1H-pyrazolo[1,2-a]pyridazin-1-onehydrochloride E

1.3 g of3-amino-2-nitroso-5,6,7,8-tetrahydro-1H-pyrazolo[1,2-a]pyridazin-1-one(compound D) and 250 mg of 5% palladium on carbon were introduced into a300 ml autoclave containing 250 ml of ethanol. The reduction was carriedout with stirring at 2000 rpm, at a temperature of 60° C. and at ahydrogen pressure of 6 bar. At the end of 2 hours of reaction, there wasno further consumption of hydrogen and the medium was cooled to 20° C.

The catalyst was removed by filtration under nitrogen after cooling toroom temperature and the solution was poured over 75 ml of hydrochloricdioxane.

The solution thus obtained was evaporated until a slightly yellow powderwas obtained which was recovered in diisopropyl ether.

The solid was recovered by filtration. After drying under vacuum in thepresence of phosphorus pentoxide, 1.1 g of2,3-diamino-5,6,7,8-tetrahydro-1H-pyrazolo[1,2-a]pyridazin-1-onehydrochloride were obtained.

The NMR spectra (¹H 400 MHz and ¹³C 100.61 MHz DMSO d₆) and mass spectraare in conformity with the expected structure E.

Examples of Dye Examples 1 to 3 Dye in an acidic medium using2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one

The following dyeing compositions were prepared: Example 1 2 32,3-Diamino-6,7-dihydro- 10⁻³ mol 10⁻³ mol 10⁻³ mol 1H,5H-pyrazolo[1,2-a]pyrazol-1-one dihydrochloride 5-Amino-2-methylphenol 10⁻³ mol 2-(2,4-10⁻³ mol Diaminophenoxy)ethanol, hydrochloride 3-Amino-2-chloro-6- 10⁻³mol methylphenol, hydrochloride Dye carrier (1) (*) (*) (*)Demineralized water q.s. 100 g 100 g 100 g(*): dye carrier (1) pH 7

Ethyl alcohol at 96% 20.8 g Sodium metabisulphite as an aqueous solutionat 35% 0.23 g A.M. Pentasodium salt of diethylene-triaminepentaaceticacid 0.48 g A.M. as an aqueous solution at 40% C₈-C₁₀ alkylpolyglucoside as an aqueous solution at  3.6 g A.M. 60% Benzyl alcohol 2.0 g Polyethylene glycol containing 8 ethylene oxide units  3.0 gNa₂HPO₄ 0.28 g KH₂PO₄ 0.46 g“A.M.” means active material.

At the time of use, each composition was mixed with an equal weight ofhydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 wasobtained.

Each mixture obtained was applied to locks of grey hair which were 90%white. After an exposure time of 30 minutes, the locks were rinsed,washed with a standard shampoo, rinsed again and then dried.

The shades obtained are presented in the table below: Example 1 2 3Shade observed chromatic intense chromatic orange chromatic orange red

Examples 4 to 6 Dye in an alkaline medium using2,3-diamino-6,7-dihydro-1H,5H-Pyrazolo[1,2-a]pyrazol-1-one

The following dyeing compositions were prepared: Example 4 5 62,3-Diamino-6,7-dihydro- 10⁻³ mol 10⁻³ mol 10⁻³ mol 1H,5H-pyrazolo[1,2-a]pyrazol-1-one dihydrochloride 5-Amino-2-methylphenol 10⁻³ mol 2-(2,4-10⁻³ mol Diaminophenoxy)ethanol, hydrochloride 3-Amino-2-chloro-6- 10⁻³mol methylphenol, hydrochloride Dye carrier (2) (*) (*) (*)Demineralized water q.s. 100 g 100 g 100 g(*): dye carrier (2) pH 9.5

Ethyl alcohol at 96% 20.8 g Sodium metabisulphite as an aqueous solutionat 35% 0.23 g A.M. Pentasodium salt of diethylene-triaminepentaaceticacid 0.48 g A.M. as an aqueous solution at 40% C₈-C₁₀ alkylpolyglucoside as an aqueous solution at  3.6 g A.M. 60% Benzyl alcohol 2.0 g Polyethylene glycol containing 8 ethylene oxide units  3.0 gNH₄Cl 4.32 g Ammonium hydroxide containing 20% of NH₃ 2.94 g“A.M.” means active material.

At the time of use, each composition was mixed with an equal weight ofhydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 wasobtained.

Each mixture obtained was applied to locks of grey hair which were 90%white. After an exposure time of 30 minutes, the locks were rinsed,washed with a standard shampoo, rinsed again and then dried.

The shades obtained are presented in the table below: Example 4 5 6Shade observed chromatic chromatic chromatic orange red orange

1-52. (canceled)
 53. A method for preparing a compound of formula (I):

wherein: R₁, R₂, R₃ and R₄, which are identical or different, are eachchosen from: linear and branched C₁-C₆ alkyl radicals optionallysubstituted with at least one radical chosen from a radical OR₅, aradical NR₆R₇, a carboxyl radical, a sulphonic radical, a carboxamidoradical CONR₆R₇, a sulphonamido radical SO₂NR₆R₇, heteroaryl radicals,and aryl radicals optionally substituted with at least one radicalchosen from (C₁-C₄)alkyl, hydroxyl, C₁-C₂ alkoxy, amino, and(di)alkyl(C₁-C₂)amino radicals; aryl radicals optionally substitutedwith at least one radical chosen from (C₁-C₄)alkyl, hydroxyl, C₁-C₂alkoxy, amino, and (di)alkyl(C₁-C₂)amino radicals; and 5- and 6-memberedheteroaryl radicals optionally substituted with at least one radicalchosen from (C₁-C₄)alkyl and (C₁-C₂)alkoxy radicals; or alternatively,R₃ and R₄ are each a hydrogen atom; R₅, R₆ and R₇, which are identicalor different, are each chosen from a hydrogen atom; linear and branchedC₁-C₄ alkyl radicals optionally substituted with at least one radicalchosen from a hydroxyl radical, C₁-C₂ alkoxy radicals, a carboxamidoradical CONR₈R₉, a sulphonyl radical SO₂R₈, and aryl radicals optionallysubstituted with at least one radical chosen from (C₁-C₄)alkyl,hydroxyl, C₁-C₂ alkoxy, amino, and (di)alkyl(C₁-C₂)amino radicals; andaryl radicals optionally substituted with at least one radical chosenfrom (C₁-C₄)alkyl, hydroxyl, C₁-C₂ alkoxy, amino, and(di)alkyl(C₁-C₂)amino radicals; or alternatively R₆ and R₇, which areidentical or different, are each chosen from a carboxamido radicalCONR₈R₉ and a sulphonyl radical SO₂R₈; R₈ and R₉, which are identical ordifferent, are each chosen from a hydrogen atom; and linear and branchedC₁-C₄ alkyl radicals optionally substituted with at least one radicalchosen from hydroxyl and C₁-C₂ alkoxy radicals; wherein at least one ofR₁ and R₂, and R₃ and R₄, may form, together with the nitrogen atoms towhich they are attached, a heterocycle chosen from saturated andunsaturated 5- to 7-membered heterocycles optionally substituted with atleast one entity chosen from halogen atoms and amino,(di)alkyl(C₁-C₄)amino, hydroxyl, carboxyl carboxamido and (C₁-C₂)alkoxyradicals, and C₁-C₄ alkyl radicals optionally substituted with at leastone radical chosen from hydroxyl, amino, (di)alkylamino, alkoxy,carboxyl and sulphonyl radicals; and R₃ and R₄ may also form, togetherwith the nitrogen atom to which they are attached, a 5- or 7-memberedheterocycle whose carbon atoms are optionally replaced with at least oneoptionally substituted atom chosen from optionally substituted oxygenand nitrogen atoms, said method comprising: a) reaction 1: reacting acompound aR₁HN—NHR₂  a  with a compound b:

to give a compound 5-amino-1,2-dihydropyrazol-3-one c:

b) reaction 2: reacting the derivative c thus obtained with anaryldiazonium salt (Ar—N₂ ^(⊕)Y^(⊖)) to give an azo compound f:

c) reaction 3: optionally functionalizing the primary amine group of theresulting azo compound f to give the following compound g:

d) reaction 4: carrying out a reaction of reduction of the azo compoundf or g to obtain an amine-containing compound e or h respectively:


54. A method for preparing a compound of formula (I):

wherein: R₁, R₂, R₃ and R₄, which are identical or different, are eachchosen from: linear and branched C₁-C₆ alkyl radicals optionallysubstituted with at least one radical chosen from a radical OR₅, aradical NR₆R₇, a carboxyl radical, a sulphonic radical, a carboxamidoradical CONR₆R₇, a sulphonamido radical SO₂NR₆R₇, heteroaryl radicals,and aryl radicals optionally substituted with at least one radicalchosen from (C₁-C₄)alkyl, hydroxyl, C₁-C₂ alkoxy, amino, and(di)alkyl(C₁-C₂)amino radicals; aryl radicals optionally substitutedwith at least one radical chosen from (C₁-C₄)alkyl, hydroxyl, C₁-C₂alkoxy, amino, and (di)alkyl(C₁-C₂)amino radicals; and 5- and 6-memberedheteroaryl radicals optionally substituted with at least one radicalchosen from (C₁-C₄)alkyl and (C₁-C₂)alkoxy radicals; or alternatively,R₃ and R₄ are each a hydrogen atom; R₅, R₆ and R₇, which are identicalor different, are each chosen from a hydrogen atom; linear and branchedC₁-C₄ alkyl radicals optionally substituted with at least one radicalchosen from a hydroxyl radical, C₁-C₂ alkoxy radicals, a carboxamidoradical CONR₈R₉, a sulphonyl radical SO₂R₈, and aryl radicals optionallysubstituted with at least one radical chosen from (C₁-C₄)alkyl,hydroxyl, C₁-C₂ alkoxy, amino, and (di)alkyl(C₁-C₂)amino radicals; andaryl radicals optionally substituted with at least one radical chosenfrom (C₁-C₄)alkyl, hydroxyl, C₁-C₂ alkoxy, amino, and(di)alkyl(C₁-C₂)amino radicals; or, alternatively, R₆ and R₇, which areidentical or different, are each chosen from a carboxamido radicalCONR₈R₉ and a sulphonyl radical SO₂R₈; R₈ and R₉, which are identical ordifferent, are each chosen from a hydrogen atom; and linear and branchedC₁-C₄ alkyl radicals optionally substituted with at least one radicalchosen from hydroxyl and C₁-C₂ alkoxy radicals; wherein at least one ofR₁ and R₂, and R₃ and R₄, may form, together with the nitrogen atoms towhich they are attached, a heterocycle chosen from saturated andunsaturated 5- to 7-membered heterocycles optionally substituted with atleast one entity chosen from halogen atoms and amino,(di)alkyl(C₁-C₄)amino, hydroxyl, carboxyl carboxamido and (C₁-C₂)alkoxyradicals, and C₁-C₄ alkyl radicals optionally substituted with at leastone radical chosen from hydroxyl, amino, (di)alkylamino, alkoxy,carboxyl and sulphonyl radicals; and R₃ and R₄ may also form, togetherwith the nitrogen atom to which they are attached, a 5- or 7-memberedheterocycle whose carbon atoms are optionally replaced with at least oneoptionally substituted atom chosen from optionally substituted oxygenand nitrogen atoms, comprising: a) reaction 1: reacting the followingcompound al:

 with a compound a2:

 to give a compound a3:

wherein: R₁₀ is chosen from a hydrogen atom, a carboxyl radical, acarboxamido radical; and C₁-C₄ alkyl radicals optionally substitutedwith at least one radical chosen from hydroxyl, amino, (di)alkylamino,alkoxy, carboxyl and sulphonyl radicals; R₁₁ and R₁₂, which areidentical or different, are each chosen from hydrogen and halogen atoms;an amino radical; (di)alkyl(C₁-C₄)amino radicals; a hydroxyl radical; acarboxyl radical; a carboxamido radical; (C₁-C₂)alkoxy radicals; C₁-C₄alkyl radicals optionally substituted with at least one radical chosenfrom hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl and sulphonylradicals; X is chosen from halogen atoms and alkyl sulphonates; r is aninteger ranging from 1 to 3; b) reaction 2: reacting the compound a3with an amine of formula NHR₃R₄ to give a compound a4:

c) reaction 3: reacting the compound a4 with at least one compoundchosen from alkylsulphonyl, arylsulphonyl and perfluoroalkylsulphonylhalides R—O₂S—X₁, wherein R is chosen from alkyl, aryl andperfluoroalkyl radicals, and X₁ is chosen from halogen atoms, in anaprotic solvent in order to give a compound a5:

d) reaction 4: heating the resulting compound a5 in a solvent having aboiling point ranging from 60° C. to 190° C. to give a compound a6:

e) reaction 5: reducing the compound a6 obtained to give the compound a7of formula (III) below:


55. The method according to claim 53, wherein R₁ and R₂ are chosen fromC₁-C₄ alkyl radicals optionally substituted with at least one radicalchosen from hydroxyl, (C₁-C₂)alkoxy, amino, and (di)alkyl(C₁-C₂)aminoradicals; and a phenyl radical.
 56. The method according to claim 55,wherein R₁ and R₂ are chosen from methyl, ethyl, 2-hydroxyethyl,3-hydroxypropyl, 2-hydroxypropyl and phenyl radicals.
 57. The methodaccording to claim 53, wherein R₁ and R₂ form, together with thenitrogen atoms to which they are attached, a ring chosen from saturatedand unsaturated optionally substituted 5- and 6-membered rings.
 58. Themethod according to claim 53, wherein R₁ and R₂ form, together with thenitrogen atoms to which they are attached, a pyrazolidine orpyridazolidine ring optionally substituted with at least one radicalchosen from C₁-C₄ alkyl, hydroxyl, (C₁-C₂)alkoxy, carboxyl, carboxamido,amino, and (di)alkyl(C₁-C₂)amino radicals.
 59. The method according toclaim 53, wherein R₁ and R₂ form, together with the nitrogen atoms towhich they are attached, a pyrazolidine or pyridazolidine ring.
 60. Themethod according to claim 53, wherein R₃ and R₄ are chosen from ahydrogen atom; linear and branched C₁-C₄ alkyl radicals optionallysubstituted with at least one radical chosen from hydroxyl,(C₁-C₂)alkoxy, amino, and (di)alkyl(C₁-C₂)amino radicals; and a phenylradical optionally substituted with at least one radical chosen fromhydroxyl, amino and (C₁-C₂)alkoxy radicals.
 61. The method according toclaim 53, wherein R₃ and R₄ are chosen from a hydrogen atom, and methyl,ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl and2-carboxyethyl radicals.
 62. The method according to claim 61, whereinR₃ and R₄ are each a hydrogen atom.
 63. The method according to claim53, wherein R₃ and R₄ form, together with the nitrogen atom to whichthey are attached, a 5- or 7-membered ring chosen from pyrrolidine,piperidine, homopiperidine, piperazine and homopiperazine heterocycles;wherein said ring is optionally substituted with at least one radicalchosen from hydroxyl, amino, (di)alkyl(C₁-C₂)amino, carboxyl andcarboxamido radicals, and C₁-C₄ alkyl radicals optionally substitutedwith at least one radical chosen from hydroxyl, amino, and C₁-C₂(di)alkylamino radicals.
 64. The method according to claim 53, whereinR₃ and R₄ form, together with the nitrogen atom to which they areattached, a 5- or 7-membered ring chosen from pyrrolidine,2,5-dimethylpyrrolidine, pyrrolidine-2-carboxylic acid,3-hydroxypyrrolidine-2-carboxylic acid,4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine,3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine,3-hydroxy-2-carboxamidopyrrolidine, 2-(diethylcarboxamido)pyrrolidine,2-hydroxymethylpyrrolidine, 3,4-dihydroxy-2-hydroxymethylpyrrolidine,3-hydroxypyrrolidine, 3,4-dihydroxypyrrolidine, 3-aminopyrrolidine,3-methylaminopyrrolidine, 3-dimethylaminopyrrolidine,4-amino-3-hydroxypyrrolidine,3-hydroxy-4-(2-hydroxyethyl)aminopyrrolidine, piperidine,2,6-dimethyl-piperidine, 2-carboxypiperidine, 2-carboxamidopiperidine,2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine,3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine,homopiperidine, 2-carboxyhomopiperidine, 2-carboxamido-homopiperidine,homopiperazine, N-methylhomopiperazine, andN-(2-hydroxyethyl)homopiperazine.
 65. The method according to claim 53,wherein R₃ and R₄ form, together with the nitrogen atom to which theyare attached, a 5- or 7-membered ring chosen from pyrrolidine,3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-dimethylaminopyrrolidine,pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid,piperidine, hydroxypiperidine, homopiperidine, diazepane,N-methylhomopiperazine, and N-β-hydroxyethylhomopiperazine.
 66. Themethod according to claim 53, wherein R₃ and R₄ form, together with thenitrogen atom to which they are attached, a 5-membered ring.
 67. Themethod according to claim 66, wherein the 5-membered ring is chosen frompyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, and3-dimethylaminopyrrolidine.
 68. The method according to claim 53,wherein the diamino-N,N-dihydropyrazolone derivatives of formula (I) andthe addition salts and solvates thereof are chosen from4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4-amino-5-methylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4-amino-5-dimethylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4-amino-5-(2-hydroxyethyl)amino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4-amino-5-(pyrrolidin-1-yl)-1,2-dimethyl-1,2-dihydropyrazol-3-one,4-amino-5-(piperidin-1-yl)-1,2-dimethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,4-amino-5-methylamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,4-amino-5-dimethylamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,4-amino-5-(2-hydroxyethyl)amino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,4-amino-5-(pyrrolidin-1-yl)-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,4-amino-5-(piperidin-1-yl)-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-phenyl-1,2-dihydropyrazol-3-one,4,5-diamino-1-ethyl-2-methyl-1,2-dihydropyrazol-3-one,4,5-diamino-2-ethyl-1-methyl-1,2-dihydropyrazol-3-one,4,5-diamino-1-phenyl-2-methyl-1,2-dihydropyrazol-3-one,4,5-diamino-1-(2-hydroxyethyl)-2-methyl-1,2-dihydropyrazol-3-one,4,5-diamino-2-(2-hydroxyethyl)-1-methyl-1,2-dihydropyrazol-3-one,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-methylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(2-hydroxypropyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-bis(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(3-hydroxypyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(piperidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-6-methyl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-6-dimethyl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one, and2,3-diamino-5,8-dihydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one.
 69. Themethod according to claim 53, wherein the diamino-N,N-dihydropyrazolonederivatives of formula (I) and the addition salts and solvates thereofare chosen from 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,and 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one.